Molybdenum-containing lubricant additive compositions, and processes for making and using same

ABSTRACT

The invention relates to an improved process for producing organomolybdenum compositions with high molybdenum content that are highly useful as lubricant additives, in which the process involves reacting a fatty oil with a diamine, followed by reaction with a molybdenum source. The process of the present invention does not require a volatile organic solvent to promote molybdenum incorporation and produces an organomolybdenum composition having a high molybdenum content. In addition, the process can be conducted in the absence of sulfur and phosphorus-containing reactants.

TECHNICAL FIELD

The present invention relates to organomolybdenum compositions havinghigh molybdenum content, which are useful as lubricant additives. Theorganomolybdenum compositions of the present invention are the reactionproducts of a fatty oil reacted with a diamine, followed by furtherreaction of the resulting intermediate with a molybdenum source to formthe organomolybdenum product compositions, in which the process does notrequire a volatile organic solvent to promote and achieve highmolybdenum incorporation in the additive product, nor does it requiresulfur-containing or phosphorus-containing reactants nor post-reactionfiltration removal for unreacted molybdenum source reactant.

BACKGROUND OF THE INVENTION

Lubricating oils used in the internal combustion engines of automobilesor trucks are subjected to a demanding environment during use. Amongother adverse effects, this environment can lead to oxidativedegradation of the oil. This oxidation of the oil is catalyzed by thepresence of certain impurities in the oil, such as iron compounds. Thisoxidation also is promoted by the elevated temperatures to which the oilis subjected during use. The oxidation of lubrication oils during use isusually controlled in part by the use of antioxidant additives, whichmay extend the useful life of the oil, particularly by reducing orinhibiting unacceptable increases in the viscosity of the oil.

Various molybdenum compounds have been used and proposed asperformance-enhancing additives for lubricant compositions. Forinstance, there are numerous examples in the patent literature whichdescribe the use of molybdenum additives variously as antioxidants,deposit control additives, anti-wear additives and friction modifiers,in lubricant compositions. A partial list of such patent referencesincludes, for example, U.S. Pat. Nos. 4,164,473, 5,840,672, 6,103,674,6,174,842, and U.S. Reissued Pat. No. RE37,363 E, among others.

The preparation of organomolybdenum additives generally requirescomplicated reaction steps that add considerable cost to themanufacturing of these additives. Examples of some costly processingsteps in this respect are as follows:

1. The use of volatile organic compound (“VOC”) solvents, such astoluene, xylenes, 2-propanol, and dimethylformamide add considerablecost to the production of organomolybdenum compounds.

2. Low levels of molybdenum incorporation into the lubricant additiveitself are achieved, which increases cost because higher concentrationsof the resulting organomolybdenum product/additive must be used in theoil to deliver the required level of molybdenum to the crankcase packageor finished oil. Ideally, it would be desirable to produce theseorganomolybdenum products/additives having molybdenum contents above 8percent by weight, and preferably above 10 percent by weight.

3. Filtration is generally required to remove unreacted inorganicmolybdenum. Unreacted molybdenum adds considerable cost to theproduction of organomolybdenum compounds because inorganic molybdenum isan expensive raw material.

4. Other costly processing steps associated with prior schemes forproducing organomolybdenum components or lubricant additives include theneed for acid or base neutralizations, the use of expensive catalysts orpromoters, and water washes.

Examples of such prior processes for making organomolybdenum componentsor lubricant additives are reported, for example, in the patentliterature as follows:

EP 1 136 496 discloses a product derived from methylaminopropylamine (Rcontains 1 carbon), which shows limited solubility in oil, whileproducts containing 6 or more carbons in the R group have low molybdenumcontent (less than or equal to 8% undiluted).

EP 1 136 497 discloses molybdenum compounds derived from carboxylicacids and glycerides, which are relatively expensive.

U.S. Pat. No. 4,889,647 discloses molybdenum products that haverelatively low molybdenum contents, for example 6 percent by weight, orlower.

U.S. Pat. No. 6,103,674 discloses molybdenum products that have lowmolybdenum contents, for example, 8 percent by weight or lower, andwhich contain sulfur.

Sulfur can be an undesirable component in engine oils. At hightemperatures and under severe conditions, even the less aggressive formsof sulfur can cause corrosion, and in some cases elastomeric sealincompatibility (e.g., rubber hardening). Ideally, therefore, molybdenumcompounds intended for use in lubricant engine oils should have minimalsulfur content.

U.S. Pat. No. 4,692,256 discloses a process for making anorganomolybdenum compound that requires neutralization steps and waterseparations in order to isolate the organomolybdenum compound. Whenwater is used as a promoter, as in U.S. Pat. No. 4,692,256, a filtrationis required to remove unreacted molybdenum.

U.S. Pat. No. 5,137,647 discloses a sulfur and phosphorous-freeorganomolybdenum complex of organic amide, such as molybdenum containingcompounds prepared from the reaction of fatty derivatives of2-(2-aminoethyl)aminoethanol with a molybdenum source, in which thereaction temperature can be as high as 160° C. The sole example providedtherein has a reaction temperature ranging from 130° C. to 140° C., anda filtration is carried out. Also, the reaction product is filtered,which adds an additional processing step.

U.S. Pat. No. 4,765,918 discloses molybdenum-containing compositionsderived from fatty oils, amines, and a sulfur source.

U.S. Pat. No. 5,412,130 discloses molybdenum products derived fromspecially pre-treated fatty oils, e.g., treated by epoxidation followedby alkylation, that are reacted with molybdenum using a very specificfatty oil-derived catalyst. This special pre-treatment of the fatty oiladds considerable cost to the resulting product, making it impracticalfor use in lubricants.

The above problems suggest a previously unfulfilled need in thelubricant additive and composition industry and related technologies foroil soluble, sulfur-free molybdenum additives having high molybdenumcontent and low tendency to discolor finished oils without the need touse volatile solvents and without the need to remove non-reactedmolybdenum. It has unexpectedly been found that the molybdenum additivesof the present invention provide the above benefits to lubricatingcompositions without the attendant problems.

SUMMARY OF THE INVENTION

The present invention is directed to unique organomolybdenumcompositions, which are especially useful as lubricant additives. Toform the organomolybdenum compositions of this invention, a fatty oil, adiamine and a molybdenum source are combined in the absence of avolatile organic solvent yet effective to form a high organo molybdenumcontent reaction product. This reaction product obtained also does nothave to be filtered to remove unreacted molybdenum source material.

In a more particular aspect, the present invention is directed to anorganomolybdenum composition comprising the reaction product of a fattyoil reacted with an aliphatic diamine, followed by further reaction ofthe resulting intermediate reaction product with a molybdenum source inthe absence of volatile organic solvent and without need forpost-reaction filtering. In one preferred aspect, the first process stepis performed neat, while in the second process step a small amount ofwater, but no volatile organic solvent is introduced or present duringthe molybdenum incorporation reaction, sufficient for the molybdenumsource ingredient to go into solution such that reaction still proceedswell.

In one further aspect, the diamine reactant used is a monsubstitutedamine having high hydrocarbon character, such as represented by thefollowing general structure:

where x is 1 or 2, and R is a hydrocarbon-containing group containing atleast about 6 carbon atoms. In one preferred aspect, the R group alsocontains oxygen, such as where R represents an alkyloxyalkylene group.

In another aspect, this invention provides a low cost process forproducing sulfur- and phosphorus-free organomolybdenum compositions withhigh molybdenum content. In one aspect, the high molybdenum content ofthe reaction products of the process of the invention comprises fromabout 8 wt % to about 15 wt % molybdenum content (Mo). In addition, theprocess improvements achieved do not require the use and presence of avolatile organic solvent to achieve highly effective incorporation ofmolybdenum in the reaction product, and the resulting reaction productalso does not require filtration to remove unreacted molybdenum sourcematerial such as molybdenum trioxide. The molybdenum-containinglubricant additives of the present invention are also very effective asantioxidants and deposit control additives in crankcase oils. Also, ithas unexpectedly been found that preparation of the organomolybdenumcompositions at reduced reaction temperatures according to anotheraspect of the present invention results in an improvement in the depositcontrol performance of the reaction product when used as an additive inengine oils. The molybdenum-containing lubricant additives of thepresent invention also are light colored complexes that are not prone todiscoloration even when used at high concentrations in crankcase oils.

DETAILED DESCRIPTION OF THE INVENTION

In an embodiment of the present invention, the reaction scheme used toprepare the molybdenum additives includes a two step process. The firstincluded step involves preparing an organic ligand comprised of anaminoamide/glycerol carboxylate mixture. This mixture is prepared bycombining, mixing, contacting, or reacting (a) a fatty oil, vegetableoil, triglyceride or other glycerol ester of a higher fatty acid with(b) a mono-substituted alkylene diamine at an elevated temperature withheating. The second step involves carrying out the molybdenumincorporation.

Fatty Oils

Examples of preferred fatty or vegetable oils that may be used in theprocess of the present invention include groundnut oil, coconut oil,linseed oil, palm kernel oil, olive oil, cottonseed oil, grapeseed oil,corn oil, canola oil, palm oil, peanut oil, safflower seed oil, sesameseed oil, caster oil, rapeseed oil (low or high erucic acids), soyabeanoil, sunflower oil, herring oil, sardine oil, lard, menhaden oil, hazelnut oil, walnut oil, and tallow, and mixtures thereof. These fatty orvegetable oils can include those compounds generally known astriglycerides, which have the general structure as shown below:

where R, R′ and R″ independently represent saturated or unsaturatedaliphatic hydrocarbon groups having from about 8 to about 22 carbonatoms, and preferably are hydrocarbon chains having about 12 to about 22carbon atoms. Mono- and diglycerides, either separately or in mixtureswith one or more triglycerides, are also useful as fatty or vegetableoils in the present invention, in which the R, R′, or R″ groups presenthave the same above meaning.

The Diamine

In order to improve solubility of the organomolybdenum product in baseoils and finished oils, it is important for the mono-substituted diamineto have a high hydrocarbon character. For example, the diamine can berepresented by the following general structure:

where x is 1 or 2, and R is a hydrocarbon-containing group containing aminimum of about 6 carbon atoms. R can be aliphatic or aromatic. R, inaddition to the minimum of about 6 carbon atoms, may also containoxygen, but preferably R does not include sulfur or additional nitrogen.It is preferred that R contains a minimum of 10 carbon atoms in order tofurther improve the organomolybdenum product solubility in base oil. Themost preferred R contains an oxygen in addition to the carbons, such aswhere R is an alkyloxyalkylene group. Where R represents analkyloxyalkylene group, R can be represented by the structure —X₁—O—X₂,where X₁ is an alkylene of 2, 3 or 4 carbons and preferably is propyleneor ethylene, and X₂ is an alkyl moiety having 3 to 30 carbon atoms, morepreferably an alkyl moiety having 7 to 20 carbon atoms, and where X₂ canbe a straight or branched, saturated or partially unsaturatedhydrocarbon chain. In diamines in which R is represented by such analkyloxyalkylene group, both high incorporation of molybdenum, e.g.,greater that 8.0 wt. % molybdenum incorporation, in to complexedproduct, as well as adequate oil-solubility are well imparted to thereaction product. The use of a diamine including an R group representedby —X₁—O—X₂ as defined herein in the reaction process makes it possibleto maximize the level of molybdenum incorporation levels in the oilsoluble reaction product while performing the process without the use ofvolatile organic processing solvents.

Examples of some mono-substituted diamines that may be used includephenylaminopropylamine, hexylaminopropylamine, benzylaminopropylamine,octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine,dodecylaminoethylamine, hexadecylaminopropylamine,hexadecylaminoethylamine, octadecylaminopropylamine,octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-diaminopropane. Mono-substituted diaminesderived from fatty acids may also be used. Examples include N-cocoalkyl-1,3-propanediamine (Duomeen C), N-tallow alkyl-1,3-propanediamine(Duomeen T), and N-oleyl-1,3-propanediamine (Duomeen O), all obtainedfrom Akzo Nobel.

In order to produce an additive reaction product with a high molybdenumcontent, it is preferred to use a molar ratio of diamine to fatty oil inthe first process step varying from about 1.50:1 to 3:1. A morepreferred ratio is from about 1.75:1.0 to about 2.5:1.0.

The reaction between the fatty oil and mono-substituted diamine iscarried out according to one embodiment at a temperature between about100 and about 150° C. by combining the two materials and heating withmixing and under a nitrogen atmosphere. The preferred reactiontemperature is between 110 and 130° C. Reaction times may vary from 1hour to 6 hours. A reaction solvent, such as an organic reactionsolvent, is not required.

As mentioned supra, the second included step of the process of thepresent invention involves carrying out the molybdenum incorporation,which is described in more detail below.

Molybdenum Source

A preferred molybdenum source is molybdenum trioxide. The use ofmolybdenum trioxide results in effective molybdenum incorporation intothe organic ligand made by the aforementioned first process step, and itproduces a reaction mass by the completion of the second step that doesnot require filtration if the reaction is performed properly accordingto guidance provided herein. Any purity grade of molybdenum trioxide maybe used but high purity molybdenum trioxide is thought more likely toproduce a product that does not require filtration.

Molybdenum Incorporation

A molybdenum source, such as molybdenum trioxide, and water are added toan aminoamide/glycerol carboxylate reaction mass obtained from the firstprocess step and maintained at approximately 80° C. The molar ratio ofmolybdenum trioxide to diamine can vary from about 1:1.25 to about1.25:1, and is preferably between 1:1.25 and 1:1 in order to maximizemolybdenum content and at the same time reduce or eliminate the presenceof unreacted molybdenum trioxide, which thus reduces or eliminates theneed for filtration. The amount of water used in this second step shouldbe an amount sufficient to incorporate all the molybdenum trioxide intothe aminoamide intermediate and is generally equivalent to the amount ofmolybdenum trioxide used, but lower and higher levels of water may beused. After addition of the molybdenum trioxide and water the reactioncomponents are slowly heated to reflux temperature with gradual removalof water. Water may be removed by vacuum distillation. The reaction maybe carried out at temperatures ranging from 100° C. to 150° C., however,it has been found that temperatures below 140° C. are preferred forproducing a molybdenum compound that is highly effective as a depositcontrol additive. The most preferred reaction temperature is below 130°C. The reaction generally requires 1 to 10 hours to remove all the waterand this time will vary depending on the reaction temperature selectedand the level of vacuum applied. During the water removal a diluent maybe added to reduce the viscosity of the final product. However, adiluent is not required for the molybdenum incorporation. Preferreddiluents include non-volatile diluents such as aromatic, paraffinic, andnaphthenic process oils and base oils as well as synthetic oils andpolyalphaolefins. A main advantage of this process is that a volatileorganic solvent, such as toluene or xylenes, is not required in thesecond step for the water removal procedure or otherwise, nor are suchorganic solvents even used in the preferred embodiment.

At the end of the reaction period, the mixture is cooled and may befiltered to remove any unreacted molybdenum trioxide. Moreover, if thereaction is run optimally, filtration is not required, as tangibleamounts of unreacted molybdenum trioxide will not be present. That is,the reaction step of molybdenum incorporation goes essentially to 100%completion. It is preferred to produce a reaction mass with completemolybdenum incorporation so that no post-reaction filtration is requiredto remove any unreacted molybdenum source material such as molybdenumtrioxide. The product prepared by this process is a dark, amber wax orviscous liquid.

Further, when the molybdenum incorporation is performed at or below 130°C., improved deposit control in engine oils is achieved using theresulting additive product of the process of the invention.

The preferred combination of mono-substituted diamine, triglyceride,fatty oil or vegetable oil, and molybdenum trioxide, is that whichproduces a molybdenum content, undiluted with oil, greater than 8 wt. %,and preferably between 10 wt. % and 15 wt. %.

It is also an unexpected discovery that carrying out the molybdenumincorporation reactions at reduced temperatures improves the depositcontrol properties of the molybdenum product produced. This isdemonstrated in the examples provided herein. It is therefore preferredto carry out the molybdenum incorporation reactions between 80 and 140°C., more preferably between 100 and 125° C.

The high molybdenum content organomolybdenum compositions of the presentinvention are useful to improve deposit control, antioxidant, antiwear,and/or friction modifiying properties of lubricant oils, and likematerials. The inclusion of the present molybdenum compounds generallyremoves the need for supplementary deposit control or antioxidants,antiwear additives and the like. However, a supplementary depositcontrol, antioxidant, and/or antiwear additive may be included in thefinished oils including the molybdenum additives of the presentinvention that are less oxidatively stable or in oils that are subjectedto unusually severe conditions. The treat rates of the molybdenumadditives depend upon the desired finished lubricant properties,however, typically the additives are present in an amount so as toprovide at least about 50, and preferably from about 50 to about 1000ppm, of molybdenum to the finished product. The concentration ofmolybdenum in the lubricants according to the invention has noparticular upper limit, however, for economic reasons a maximum level ofabout 1000 ppm is generally preferred although not required.

As an important aspect of the present invention, a process for making anorganomolybdenum additive has been discovered which can be performed inthe absence of volatile organic solvent without sacrificing the level ofmolybdenum incorporation or oil solubility of the reaction product. Thisprocess thus avoids the production and handling costs that otherwisewould be associated with using such additional chemicals in performingthe process. The language “absence of volatile organic solvent” means novolatile organic solvent is intentionally introduced or otherwisepermitted to be present with the diamine, fatty oil and intermediatereaction product during the process of the present invention in amountsthat might exceed trace amounts, that is, the amount of volatile organicsolvent present, if any, during the process is less than 3.0 wt. % ofthe total reactor contents. From this standpoint, the process of thepresent invention consists essentially of the reaction product of fattyoil, diamine, and molybdenum source.

In addition, the organomolybdenum compositions of the present inventioncan be prepared without introducing sulfur or phosphorus. Theorganomolybdenum complex reaction products are substantially sulfur-freein the sense that the reaction itself introduces no sulfur into thereaction product, although some negligible trace levels of sulfur whichare not part of the molybdenum product itself might be present due toimpurities or catalysts left behind from the manufacturing process.Preferably, the amount of any sulfur in the organomolybdenum reactionproduct is less than 0.05 wt. %.

Sulfur can cause corrosion and elastomeric nitrile sealcompatibility-hardening problems, among other things, while phosphoruscan reduce automobile catalyst compatibility such as when used incrankcase oil formulations. The organomolybdenum compositions of thepresent invention can be formed free or at least substantially free ofsulfur and phosphorus because no reactants including such materials areneeded, nor used in the preferred embodiments.

When formulated into a lubricating oil, the organomolybdenum additivesof the present invention optionally can be used in combination thereinwith one or more other additives including those typically used inlubrication oils. Typical additives used in lubrication oils, whichoptionally can be used in this respect, include detergents, corrosioninhibitors, rust inhibitors, additional antioxidants, dispersants, foaminhibitors, additional antiwear agents, additional friction modifiers,demulsifiers, VI improvers, pour point depressants, zincdialkyldithiophopshates (ZDDP), and so forth. Examples of such optionalsupplemental additives are described, for example, in U.S. Pat. No.5,840,672, which teachings are incorporated herein by reference.

The organomolybdenum compositions of the present invention are “oilsoluble” in the sense that they are oil-soluble or capable of beingsolubilized under normal blending or use conditions into a lubricationoil or diluent for the concentrate.

The overall composition of a lubricating oil including theorganomolybdenum additive such as described herein can varysignificantly based on the customer and specific application. Theadditive of this invention can be employed in a variety of lubricatingoil base stocks, such as derived from natural lubricating oils,synthetic lubricating oils or mixtures thereof. These oils includetypical crankcase lubrication oils for spark-ignited andcompression-ignited internal combustion engines, for example natural gasengines, automobile and truck engines, marine, and railroad dieselengines.

These oil base stocks can include, for example, hydrocracked base oils;mineral oils such as paraffinic, naphthenic or mixtures thereof;vegetable oils; petroleum oils, oils derived from coal shale;silicon-based oils; halosubstituted hydrocarbon oils; esters ofdicarboxylic acids with alcohols; wax isomerate oils; polyalphaolefins,and mixtures thereof. In one preferred non-limiting embodiment, the baseoils used in forming the lubricating compositions of the presentinvention are characterized by the presence of a high level of saturatesand a very low level of sulfur, and include base oils referred to in thepetroleum additive industry as Group II and Group III base oils. Furtherdetails on such base oils are described, for example, in U.S. Pat. No.5,840,672, which teachings are incorporated herein by reference. In onenon-limiting illustration, the base oils generally contain greater thanor equal to 90% saturates, less than or equal to 0.03 weight percentsulfur and have a viscosity index of greater than or equal to about 80.The base oil typically has a viscosity generally of about 2 to about 15cSt at 100° C.

In one non-limiting embodiment, the lubricant oil can be a formulatedoil comprising between about 75 to about 95 weight percent (wt %) of abase oil of lubricating viscosity, between 0 and 30 wt % of a polymericviscosity index improver, between about 5 and 15 wt. % of an additionaladditive package and typically a sufficient amount of molybdenum complexto provide at least about 50 ppm of molybdenum to the finishedlubricant. The optional supplemental additives, for example, could be asupplemental detergent/inhibitor additive package and/or viscosity indeximprover. The present invention also encompasses the improvedlubricating oil compositions, which contain the organomolybdenumadditives of the present invention.

The organomolybdenum additives of the present invention can be used inlubricating oils such as crankcase oils for internal combustion engines,as well as gear lubricants, hydraulic fluids, automatic transmissionfluids, turbine lubricants, engine fuels, compressor oils, lubricatinggreases, and so forth. The lubricating oil compositions of thisinvention can be made by adding the molybdenum compositions, and anysupplemental additives, to an oil of lubricating viscosity. The methodor order of component addition is not critical. Alternatively, themolybdenum compositions, along with any additional additives, can beadded to the oil as a concentrate.

EXAMPLES

The following examples further illustrate aspects of the presentinvention but do not limit the present invention.

The attached examples demonstrate that organomolybdenum additives withundiluted molybdenum contents between 8.1 wt % and 11.4 wt % are easilyproduced using this process and inexpensive triglycerides as the fattyor vegetable oil reactant and starting material. It is possible usingthis process, and the right combination of diamine and vegetable oil,for example, to produce organomolybdenum additives with undilutedmolybdenum contents as high as 15 wt %. The examples described hereinalso show that molybdenum incorporations performed at reducedtemperature produce molybdenum additives with improved deposit controlproperties.

It has also been found that most of the organomolybdenum compoundsproduced in the examples described herein did not require filtration toremove unreacted molybdenum trioxide. Examination of filters after thefiltration process showed no evidence of collected unreacted molybdenumtrioxide or insolubles of any type in any appreciable quantities. Thusfiltration is typically not required in the practice of the additivemaking process of the present invention.

The oil-soluble molybdenum-containing additives of the present inventionmay be used as antioxidants, deposit control additives, anti-wearadditives, and/or friction modifiers. The table below summarizes treatrates and additive combinations for the various applications:

TABLE 1 Appli- Recommended Performance cation Treat Range BoostingAdditives Oil Type Anti- 75-250 Diphenylamines Passenger Car and oxidantppm Mo (0.05-1.0%) Medium Speed Sulfur Containing Diesel Oils Additives(0.2-1.0%) Sulfurized Phenate Detergents (0.3-3.0%) ZDDP (0.5-1.2%)Anti-wear 50-100 ZDDP Sulfur Passenger Car and ppm Mo ContainingAdditives Heavy Duty Diesel Oils Deposit 75-250 Diphenylamines HeavyDuty Diesel Control ppm Mo (0.05-1.0%) and Natural Gas SulfurizedPhenate Engine Oils Detergents (0.2-3.0%) Friction 250-1000 AntioxidantsPassenger Car Oils Modifier ppm Mo (0.1-1.0%) Organic Friction Modifiers(0.3-1.0%)

Example 1 Preparation of Sulfur-Free Organomolybdenum Additive (SampleNo. 1)

A. Preparation of Amide Organic Ligand Intermediate Reaction Product

RBD Canola Oil (250.0 g, 0.277 mol) was added to a 500 mL resin kettleequipped with a reflux condenser, an addition funnel, a thermometer, amechanical stirrer, and a heating mantle. Dry nitrogen was passed intothe reactor through the addition funnel, and out of the reactor throughthe reflux condenser. The Canola Oil was heated to 80° C. andisodecyloxypropyl-1,3-diaminopropane (135.0 g, 0.458 mol) was addeddropwise over 45 minutes. During the amine addition the reactiontemperature was held at 80° C. The reaction mixture was then heated to125° C. and held at that temperature, under nitrogen and with sufficientagitation, for 5½ hours. The reaction was cooled overnight.

B. Molybdenum Incorporation—Preparation of Organomolybdenum DerivativeComplex Product

The amide mixture intermediate reaction product, prepared as describedabove, was heated to 80° C. and the molybdenum trioxide (66.0 g, 0.459mol) and water (35.0 g, 1.94 mol) are added. The reaction mixturerapidly rose to 95° C. The reaction mixture was then heated to refluxtemperature and held at 111° C. for 30 minutes. Water was collected to areaction temperature of 130° C. Shell E-C 100 N process oil (96.6 g) wasthen added. Vacuum was applied and the remaining water was removed at130° C. over a 5 hour period. The resulting product was cooled to 100°C. and filtered using a pressure filtration apparatus. The product wasisolated as an amber viscous oil. Weight of Product Collected=520 g. Thephysical and chemical properties of the organomolybdenum product are asfollows: Viscosity @ 100° C.=71.93 cSt, Nitrogen Content=2.611 wt %,Molybdenum Content=8.298 wt %, Calculated Molybdenum Undiluted=10.1 wt%, TBN (ASTM D 2896)=32.3 mg KOH/g, IR Carbonyl Stretches=1738 cm⁻¹,1639 cm⁻¹.

Preparation of Organomolybdenum Additive Sample Nos. 2-9

Additional samples of sulfur- and phosphorus-free organomolybdenumadditives were prepared in a manner analogous to that described above,with modifications, reagents, reaction conditions, and properties asdefined in the table below:

TABLE 2 Additive Sample No. 2 3 4 5 6 7 8 9 Canola Oil (g) 225.0 270.0225.0 225.0 300.0 250.0 — 337.5 Coconut Oil (g) — — — — — — 190.0 —Diamine (g)¹ — — 135.0 135.0 123.3 135.0 135.0 202.5 Diamine (g)² 115.0114.0 — — — — — — MoO₃ (g) 50.0 49.2 51.0 65.0 59.3 71.5 66.0 98.0 Water(g) 25.0 25.0 25.0 35.0 30.0 35.0 35.0 52.5 Process Oil (g) 127.0 76.2None 104.0 None 140.2 156.6 175.0 Yield (g) 497 492 377 499 456 545 530774 Mo Rx Temp. Range 80-120 80-120 80-120 80-125 80-130 80-140 80-14080-140 (° C.) Visc. @ 100° C. (cSt) 55.0 66.3 100.4 78.9 103.2 53.8 55.167.5 Molybdenum (wt %) 6.61 6.62 8.39 8.28 8.13 8.34 8.06 8.24 Calc MoUndiluted 8.8 7.8 8.4 10.4 8.1 11.0 11.4 10.6 (wt %) Nitrogen (wt %)2.40 2.44 3.40 2.66 2.65 2.38 2.64 — TBN (mg KOH/g) 43.1 39.9 47.4 39.636.0 28.3 30.8 34.2 IR carbonyl (cm⁻¹) 1739, 1739, 1738, 1739, 1739,1739, 1738, 1738, 1639 1640 1639 1640 1639 1639 1638 1638¹Isodecyloxypropyl-1,3-diaminopropane ²N-coco-1,3-diaminopropane

Preparation of Organomolybdenum Additive Sample No. 10

As an additional additive sample which was prepared, sample no. 10,2-(2-aminoethylamino)ethanol was instead used as the diamine reactant.For this additional study, Step A, the preparation of the amide organicligand was conducted in the same manner as described above except that225.0 g (0.25 mol) of canola oil was used as the fatty oil reactant, and47.7 g (0.458 mol) of 2-(2-aminoethylamino)ethanol was used as thediamine reactant. In step B, the molybdenum incorporation step, theamide mixture intermediate reaction product obtained from step A washeated to 80° C. and the molybdenum trioxide (65.0 g, 0.45 mol) andwater (35.0 g, 1.94 mol) are added. The reaction mixture rapidly rose to91° C. The reaction mixture was heated to reflux temperature to removewater. Excessive foaming was observed to occur at 102° C. Heating wascontinued and the foaming was observed to get considerably worse. Twodrops of Dow Corning Fluid 20% was added to the reaction in an attemptto reduce the foaming. No reduction in foaming was observed. At thispoint the foaming was to the extent that the reaction mass started toclimb out of the reactor, at which point the heating procedure wasterminated. The heating mantle was removed while the reactiontemperature was still above 100° C. Considerable foam was observed inthe reaction product mass. Thus, the additive samples 1-9, which wereperformed without an organic reaction solvent and did not require anyextraneous antifoaming agents, are preferable over additive sample 10.

Example 2 Evaluation of Organomolybdenum Additives in the CaterpillarMicro-Oxidation Test

Organomolybdenum complexed product samples 1-9, as prepared in Example1, were evaluated as additives in a modified version of the CaterpillarMicro-Oxidation Test (CMOT). Each additive was added to a separateamount of SAE grade 15W-40 fully formulated crankcase oil containingapproximately 1000 ppm of phosphorus derived from ZDDP and 0.5 weight %of an alkylated diphenylamine antioxidant. This provided test Oils 1-9.A Comparison Oil was also tested in which the crankcase oil contained nomolybdenum additive. The particular organomolybdenum complexed productamong samples 1-9 used in each sample of base oil is indicated in Table3. The additive treat levels were such that approximately 160 to 170 ppmof molybdenum was delivered to the respective finished Oils 1-9. Foradditives in the 8% molybdenum content range, this corresponds to 0.20wt % of additive added to the lubricating oil formulation. For additivesin the 6.5% content range, this corresponds to 0.25 wt % of additivecontent in the lubricating oil formulation.

The Micro-Oxidation Test is a commonly used technique for evaluating thedeposit forming tendencies of a wide variety of passenger car and diesellubricants as well as mineral and synthetic basestocks. The testmeasures the oxidative stability and deposit forming tendencies oflubricants under high temperature thin-film oxidation conditions. Theability to easily vary test conditions and the flexibility of presentingtest results makes it a valuable research tool for screening a widevariety of lubricant products. In this test, a thin-film of finished oilis accurately weighed onto an indented low carbon steel sample holdersitting in a glass impinger tube. The sample, coupon and impinger tubeassembly is then immersed in a high temperature bath. Dry air is passed,at a specific rate, through the impinger tube, over the oil sample, andout of the impinger tube to the atmosphere. At specific time intervalsthe carbon steel sample holders are removed from the high temperaturebath, rinsed with solvent to remove any remaining oil, and oven dried.The solvent washes are filtered to collect any deposits that dislodgefrom the carbon steel holders. The sample holders and collected depositsare weighed to determine the amount of deposit formed at the samplinginterval. Results are reported as the percent of oil sample formingdeposit at a specific time interval. The induction time to depositformation can also be determined by calculating the intercept betweenthe baseline formed where minimal deposits are seen, and the slopeformed where a rapid rise in deposit formation is seen. Longer inductiontimes correspond to improved deposit control. Another parameter of valuein this test is the Performance Index (PI). The Performance Indexrepresents the reduction in deposit formation of the additized finishedoil over the entire sampling range of testing versus the baselinefinished oil over the same sampling range. The formula for calculatingPI is as follows:PI = [((area  of  baseline  oil/area  of  additized  oil) − 1) × 100].A  larger  Performance  Index  (PI)  corresponds  to  improved  deposit  control.

The test conditions used to evaluate the test oils 1-9 are as follows:gas=dry air, flow=20 cc/minute, temperature=230° C., samplinginterval=50, 60, 70, 80, 90, 100, 110, 120 minutes, samplesize=approximately 20 microL accurately weighed.

The deposit control results, as reported in percent deposits (wt %), forthe tested oils containing the respective organomolybdenum compounds areshown in the table below:

TABLE 3 Test Oil Comp. Oil 1 Oil 1 Oil 2 Oil 3 Oil 4 Oil 5 Oil 6 Oil 7Oil 8 Oil 9 Additive Sample No. No Mo Additive 2 3 1 4 5 6 7 8 9 Timewt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % (min) dep'sdep's dep's dep's dep's dep's dep's dep's dep's dep's Percent Deposits(wt. % dep's) as a Function of Time 50 4.4 1.4 1.9 1.1 2.1 4.2 2.0 2.61.3 3.2, 3.1 60 5.4 2.2 2.0 4.6 4.2 4.2 2.1 3.5 1.4 3.4, 3.2 70 15.3 2.32.4 6.2 4.7 4.3 2.2 3.5 1.9 3.4, 3.4 80 16.4 2.8 2.6 6.3 4.8 4.3 2.6 3.92.1 3.7, 4.1 90 19.9 2.9 3.9 6.6 4.8 7.8 6.1 4.4 6.4 8.9, 8.3 100 21.42.9 10.8 9.0 4.8 10.3 11.0 17.1 8.8 18.2, 19.5 110 30.5 6.6 11.2 14.24.8 8.8 19.9 15.7 12.7 21.6, 16.1 120 28.8 6.2 11.0 20.0 14.7 8.8 19.115.7 20.5 22.5, 15.6 Onset to Deposit Formation Min 53 101 89 96 111 8082 90 82 81, 80 Performance Index (PI) = [((area No Mo/area plus Mo)− 1) × 100] PI 421 210 109 216 170 119 114 158 67, 94

Thus, the molybdenum-containing compositions of the present inventiondemonstrate a clear trend toward improvement in deposit control in anengine. Also shown is a significant reduction in deposits when themolybdenum additives are prepared at lower reaction temperatures.

Example 3 Evaluation of Organomolybdenum Additives for Oil Coloration

A color and visual solubility were determined for the molybdenumcomplexed compounds of sample nos. 1-8, as described in Example 1, usinga paraffinic process oil diluent (PO#5). The color method was ASTM D1500. Color results are reported to the nearest one-half unit match onthe D1500 color scale. The treat levels were 1 wt. % for each testedsample, in which the treat level is based upon the amount (weightpercent) of the molybdenum compound added to the process oil, not theamount of molybdenum delivered to the process oil. An additional sample,sample no. 11, was prepared and tested in a similar manner forsolubility,and color in which the organomolybdenum complexed productused was prepared in the manner described for additive Sample M6 asdescribed in European published patent application EP 1 136 496 A1. TheM6 additive involves the reaction product of2-(2-aminoethylamino)ethanol and canola oil in which an organic reactionsolvent is used during molybdenum incorporation.

The color and oil solubility results observed for these tests aresummarized below in Table 4. The higher the D1500 color value reported,the greater the darkening of the process oil that has occurred onaccount of the addition of the organomolybdenum additive.

TABLE 4 Additive Sample No. 1 2 3 4 5 6 7 8 11 D1500 Color in PO#5 1.51.0 1.0 1.5 1.5 1.5 2.5 N/A 3.5 Solubility in PO#5 yes yes yes yes yesyes yes no yes

From an examination of the results in Table 4, it is apparent that thatthe molybdenum compounds made with diamine reactant in which the R groupsubstituent, with reference to the diamine chemical structure describedabove herein, was an alkyloxyalkylene group, such as in samples 1-7, hadthe optimal color properties. It also is apparent that the molybdenumcompounds made with canola oil reactant (i.e., in which the R, R′ and R″hydrocarbon chains therein are in the range of C₁₂ to C₂₂, withreference to the fatty oil chemical structure described above herein)had excellent oil solubility.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein. It is intended that the specificationand examples be considered as exemplary only, with a true scope andspirit of the invention being indicated by the following claims. It isto be understood that both the foregoing general description and thefollowing detailed description are exemplary and explanatory only andare intended to provide further explanation of the present invention, asclaimed. This invention is susceptible to considerable variation in itspractice. Accordingly, this invention is not limited to the specificexemplifications set forth hereinabove. Rather, this invention is withinthe spirit and scope of the appended claims, including the equivalentsthereof available as a matter of law.

The patentee does not intend to dedicate any disclosed embodiments tothe public, and to the extent any disclosed modifications or alterationsmay not literally fall within the scope of the claims, they areconsidered to be part of the invention under the doctrine ofequivalents.

What is claimed is:
 1. A composition comprising the reaction product ofa fatty oil, a diamine, and a molybdenum source in which the reactionproduct is formed in the absence of carbon disulfide and volatileorganic solvent.
 2. The composition according to claim 1, whereinmolybdenum source is molybdeum trioxide.
 3. The composition according toclaim 1, wherein the fatty oil is selected from a vegetable oil and atriglyceride, or a mixture thereof.
 4. The composition according toclaim 1, wherein the fatty oil is selected from groundnut oil, coconutoil, linseed oil, palm kernel oil, olive oil, cottonseed oil, grapeseedoil, corn oil, canola oil, palm oil, peanut oil, safflower seed oil,sesame seed oil, caster oil, rapeseed oil, soyabean oil, sunflower oil,herring oil, sardine oil, lard, menhaden oil, hazel nut oil, walnut oil,and tallow, and mixtures thereof.
 5. The composition according to claim1, wherein the fatty oil is a triglyceride having the formula:

wherein R, R′, and R″ each independently represents a saturated orunsaturated hydrocarbon chain group having about 8 to about 22 carbonatoms.
 6. The composition according to claim 1, wherein the vegetableoil comprises canola oil.
 7. The composition according to claim 1,wherein the diamine is selected from phenylaminopropylamine,hexylaminopropylamine, benzylaminopropylamine, octylaminopropylamine,octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine,hexadecylaminopropylamine, hexadecylaminoethylamine,octadecylaminopropylamine, octadecylaminoethylamine,isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-diaminopropane, mono-substituted diaminesderived from fatty acids, N-coco alkyl-1,3-propanediamine, N-tallowalkyl-1,3-propanediamine, and N-oleyl-1,3-propanediamine, and mixturesthereof.
 8. The composition according to claim 1, wherein the diaminehas the chemical structure

wherein x is 1 or 2 and R is an alkyl or alkyloxyalkylene group.
 9. Thecomposition according to claim 8, wherein R has at least 10 carbonatoms.
 10. The composition according to claim 8, wherein R furthercontains oxygen and is devoid of sulfur and nitrogen.
 11. Thecomposition according to claim 8, wherein R represents analkyloxyalkylene group.
 12. The composition according to claim 8,wherein R is represented by the structure —X₁—O—X₂, wherein X₁ is analkylene of 2, 3 or 4 carbons, and X₂ is an alkyl moiety having 3 to 30carbon atoms, and where X₂ can be a straight or branched, saturated orpartially unsaturated hydrocarbon chain.
 13. The composition accordingto claim 1, wherein the molar ratio of diamine to fatty oil is fromabout 1.5:1 to about 3:1.
 14. The composition according to claim 1,wherein the molar ratio of molybdenum to diamine is from about 1:1.25 toabout 1.25:1.
 15. The composition according to claim 1 containing lessthan 0.05 weight percent sulfur.
 16. The composition according to claim1 having a molybdenum content of from about 8.1 wt % to about 15 wt %.17. The composition according to claim 1 having a molybdenum content offrom 10.0 wt % to 15.0 wt %.
 18. An oil soluble composition comprisingthe reaction product of a fatty oil, a diamine, and a molybdenum source,wherein the diamine has the chemical structure:

wherein x is 1 or 2, and R is an alkyloxyalkylene group represented by—X₁—O—X₂, wherein X₁ is an alkylene of 2, 3 or 4 carbons, and X₂ is analkyl moiety having 3 to 30 carbon atoms, and wherein the fatty oilcomprises a triglyceride having fatty acid moieties, and said fatty acidmoieties comprise C₁₂ to C₂₂ hydrocarbon chains, and wherein the oilsoluble composition includes a molybdenum content of from about 8.1 wt %to about 15 wt %.
 19. The oil soluble composition according to claim 18,wherein the molybdenum source comprises molybdenum trioxide.
 20. The oilsoluble composition according to claim 18, wherein x is 2, X₁ is 2, 3 or4, and X₂ is an alkyl group having 3 to 20 carbon atoms.
 21. The oilsoluble composition according to claim 18, wherein the molar ratio ofdiamine to fatty oil is from about 1.5:1 to about 3:1.
 22. A compositionaccording to claim 1, said composition diluted with a process, mineralor synthetic oil.
 23. A lubricating oil composition comprising a majoramount of an oil of lubricating viscosity, and a minor amount of acomposition according to claim 1 present in an amount sufficient toprovide at least 50 ppm of molybdenum in the lubricating oilcomposition.
 24. A composition according to claim 18, said compositiondiluted with a process, mineral or synthetic oil.
 25. A process forpreparing a molybdenum-containing composition, comprising reacting afatty oil, a diamine, and a molybdenum source, in the absence of carbondisulfide and volatile organic solvent.
 26. The process according toclaim 25, which comprises: (a) reacting a fatty oil with a diamine toform an intermediate reaction mixture, and (b) adding a molybdenumsource to thus obtained intermediate reaction mixture, wherein (a) and(b) are performed without introducing volatile organic solvent.
 27. Theprocess according to claim 26, wherein the intermediate reaction mixturecomprises an aminoamide/glycerol carboxylate mixture prepared bycombining a glycerol ester of a fatty acid selected from a fatty oil,vegetable oil, triglyceride, or a mixture thereof, with amono-substituted alkylene diamine.
 28. The process according to claim27, further comprising incorporating molybdenum into the intermediatereaction mixture by combining a molybdenum source with theaminoamide/glycerol carboxylate mixture.
 29. The process according toclaim 27, further comprising combining and heating the glycerol ester ofa fatty acid and the mono-substituted alkylene diamine with mixing at atemperature between about 100 degrees Celsius and about 150 degreesCelsius.
 30. The process according to claim 27, wherein the molybdenumsource is molybdenum trioxide.
 31. The process according to claim 27,wherein the molybdenum source and water are combined with theaminoamide/glycerol carboxylate mixture for a time and at a temperaturesufficient to produce a molybdenum-containing reaction product.
 32. Theprocess according to claim 31, wherein the time is from 1 to about 10hours and the temperature is from about 100 degrees Celsius to about 150degrees Celsius.
 33. A composition produced by the process of claim 26.34. The composition of claim 33, wherein the composition contains lessthan 0.05 wt % sulfur.
 35. The composition of claim 33, wherein thecomposition comprises from 10.0 wt % to 15.0 wt % molybdenum.
 36. Thecomposition of claim 33, wherein the composition comprises between 8.1wt % and 11.4 wt % molybdenum.
 37. A process of lubricating a crankcasecomprising adding the composition of claim 1 to a crankcase.
 38. Acrankcase lubricated with a composition of claim
 1. 39. Anorganomolybdenum composition comprising the reaction products of (i) atleast one fatty oil; (ii) at least one mono-alkylated alkylene diamine;and (iii) a molybdenum source, wherein the organomolybdenum compositionincludes a molybdenum content of from about 8.1 wt % to about 15 wt %.40. An organomolybdenum composition comprising the reaction products of(i) at least one fatty oil; (ii) at least one mono-alkylated alkylenediamine; and (iii) a molybdenum source, wherein the molar ratio ofmolybdenum source to mono-alkylated alkylene diamine is from about 2:3to about 1.15:1.
 41. An organomolybdenum composition comprising thereaction products of (i) at least one fatty oil; (ii) at least onemono-alkylated alkylene diamine; and (iii) a molybdenum source, whereinthe total base number (TBN) as determined by ASTM D2896 is less than 50mg KOH/gram.
 42. An organomolybdenum composition comprising the reactionproducts of (i) at least one fatty oil; (ii) at least one mono-alkylatedalkylene diamine; and (iii) a molybdenum source, wherein the molar ratioof molybdenum source to mono-alkylated alkylene diamine is from about2:3 to about 1.15:1, and wherein the total base number (TBN) asdetermined by ASTM D2896 is less than 50 mg KOH/gram.
 43. A process forpreparing a molybdenum-containing composition comprising: (a) combininga material selected from the group consisting of a fatty oil, vegetableoil, a triglyceride, and glycerol ester of a fatty acid, with amono-substituted alkylene diamine to produce an aminoamide/glycerolcarboxylate mixture; and (b) combining the mixture from (a) with amolybdenum source in the presence of water.
 44. A product produced bythe process of claim 43.